JP2011148137A - Method for manufacturing inkjet recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an inkjet recording material which can continuously be mass-produced and in which fluctuation of quality is reduced during continuous producing. <P>SOLUTION: The method for manufacturing the inkjet recording material includes at least a first step for applying a coating liquid for an ink accepting layer on a supporting body and a second step for processing the coated film which becomes an ink accepting layer obtained in the first step by a processing liquid mainly containing a polar solvent stored in a processing liquid storage tank and thereafter drying the same, wherein the processing temperature of the processing liquid is 30 to 80°C, the processing time is within 3 sec. and the remaining crosslinking agent concentration in the processing liquid is 10 g/L or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a so-called wet process in which a coating liquid for an ink-receiving layer is applied on a support and then treated with a treatment liquid mainly containing an acidic solution, water, or a neutral to basic polar solvent. The present invention relates to a method for manufacturing an ink jet recording material, which is capable of continuously mass-producing such an ink jet recording material and has little quality fluctuation during the continuous production.

  As a recording material used in the ink jet recording system, an ink jet recording material in which an ink receiving layer is provided on a support is known. Such ink receiving layers are roughly classified into two types: ink receiving layers mainly composed of water-soluble polymers, and porous ink receiving layers mainly composed of inorganic fine particles and a resin binder. The former ink-receiving layer absorbs ink by swelling the water-soluble polymer, and the latter ink-receiving layer absorbs ink in voids formed by inorganic fine particles. Due to the difference in ink absorption mechanism, the former is called a swelling type (or polymer type), and the latter is called a void type (or microporous type).

  With the widespread use of digital cameras, digital photos have become familiar, and ink jet printers equipped with inks using water-soluble dyes suitable for outputting digital photo images (hereinafter referred to as dye inks) have become widespread. In recent years, the image quality and printing speed of pigment ink printers are remarkable. With the increase in resolution of such an ink jet printer, various ink jet recording materials capable of high-quality recording have been developed.

  Ink-jet recording materials for printing digital photo images are generally required to have high image quality with high ink absorbability and color developability and little blurring of printed images. For this purpose, various ink jet recording materials having the above-described void-type ink receiving layer have been developed and put into practical use. For example, Japanese Patent Publication No. 3-56552, JP-A-10-119423, 2000-212235, 2000-309157 and the like are composed of vapor-phase method silica and a water-soluble binder such as polyvinyl alcohol. An ink jet recording material provided with a void-type ink receiving layer is disclosed. JP-A-9-286165, JP-A-10-181190 and the like disclose usage examples of pulverized precipitated silica, and JP-A-2001-277712 discloses examples of use of crushed gel silica. JP-A-62-174183, JP-A-2-276670, JP-A-5-32037, JP-A-6-199034, etc. disclose examples of using alumina and alumina hydrate.

  However, there are various problems with the ink jet recording material having the above-described void-type ink receiving layer. For example, image bleeding when stored under high humidity and high temperature after printing with dye ink, front feed printer (recording media) Printer having a portion with a large curvature in the transport path), transport cracks in the ink receiving layer when transported, difference in gloss between the printed part and the non-printed part when printing with pigment ink, on the support There were problems such as cracking of the ink receiving layer when the ink receiving layer was coated on the surface.

  Regarding image bleeding when stored under high humidity and high temperature, for example, an inkjet recording material having an ink receiving layer on a support is immersed in an acidic solution and dried, as disclosed in JP-A-2004-25723 (Patent Document). In regard to improvement of pigment gloss uniformity, dye color gamut, wet bleed, etc. disclosed in 1), the media sheet for inkjet printing is washed by removing unreacted water-soluble coating formulation additives from the ink receiving layer. It is disclosed in Japanese translations of PCT publication No. 2008-538337 (patent document 2) that the conductivity is less than about 80 μS / cm. In addition, regarding the improvement of the cracks when the ink receiving layer is applied and the transparency of the ink receiving layer, a mixed solution of ammonia water and an aqueous borax solution is applied to a coat layer containing alumina or alumina hydrate and polyvinyl alcohol. Japanese Unexamined Patent Publication No. 2007-313844 (Patent Document 3) discloses removing excess borax by washing with water after gelation. Further, the applicant of the present application disclosed in Japanese Patent Application No. 2009-63001 an ink mainly containing inorganic fine particles having an average secondary particle size of 500 nm or less on a non-absorbent support, and containing a resin binder and a crosslinking agent. A first step of applying a receiving layer coating solution and ending at least constant rate drying; a second step of treating the ink receiving layer obtained in the first step with a neutral to basic solvent and then drying; It was disclosed that the ink jet recording material obtained through the above process can improve the cracking of conveyance when conveyed by a front feed printer, the difference in gloss between the blank paper portion and the pigment ink printing portion, and the like.

  In any of these methods for producing an ink jet recording material, an ink receiving layer coating solution is applied onto a support, and after the coating film is gelled or dried, an acidic solution, water, or neutral to base is used. A so-called wet treatment is used in which treatment is performed with a treatment liquid mainly containing a polar solvent having properties. On the other hand, it is generally known that the ink-jet recording material is produced by applying a coating solution for an ink receiving layer to a support of several hundred to several thousand meters wound up in a roll shape. However, according to the conventional technology, when an ink receiving layer coating solution is applied to a long support ranging from several hundred to several thousand meters and then wet-processed, a stable quality ink jet recording material is manufactured. It was extremely difficult to do.

JP 2004-25723 A Special table 2008-538337 gazette JP 2007-313844 A

  An object of the present invention is to apply a coating liquid for an ink-receiving layer on a support, and then treat with a treatment liquid mainly containing an acidic solution, water, or a neutral to basic polar solvent. A method of manufacturing an inkjet recording material subjected to a wet process, and capable of continuously mass-producing such inkjet recording material and providing a method of manufacturing an inkjet recording material with less quality fluctuation during continuous production. It is in.

The above object of the present invention has been achieved by the following invention.
1) A first step of applying a coating liquid for an ink-receiving layer on a support, and a polar solvent stored in a treatment liquid storage tank for a coating film to be an ink-receiving layer obtained in the first step. A method for producing an ink jet recording material comprising at least a second step of treatment with a treatment liquid contained therein, followed by drying, wherein the treatment temperature of the treatment liquid is 30 to 80 ° C. and the treatment time is within 3 seconds. And a concentration of the residual crosslinking agent in the treatment liquid is 10 g / L or less.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for manufacturing an inkjet recording material that can continuously mass-produce inkjet recording materials that are manufactured by performing a wet process and that has little quality fluctuation during continuous production.

Schematic which shows an example of the manufacturing apparatus typically used at the 2nd process of this invention. Schematic which shows an example of the manufacturing apparatus typically used at the 2nd process of this invention. Schematic which shows an example of the manufacturing apparatus typically used at the 2nd process of this invention.

  The present invention is described in detail below. In the production method of the present invention, the coating film to be the ink receiving layer obtained in the first step is treated with a treatment liquid mainly containing a polar solvent stored in the treatment liquid storage tank, and then dried. At least a process. The second step of the present invention is preferably performed after the coating film serving as the ink-receiving layer is gelled, and any of the constant rate drying region, the decremental drying region, and the drying end of the step of drying the coating film thereafter. Although it is possible to carry out at the stage, it is preferable to carry out after the constant rate drying region. By carrying out after the constant rate drying region, the water-soluble polymer component (for example, hydrophilic binder) contained in the coating liquid for the ink receiving layer is prevented from flowing into the processing liquid as much as possible in the second step. It is possible to prevent the ink absorbability of the resulting ink jet recording material from being lowered.

  The constant-rate dry region means that the water and solvent in the wet coating film simply evaporate while taking away the latent heat of vaporization, so the surface temperature of the wet coating film is the wet bulb temperature (water droplets in the equilibrium state of moist air). It is a region that is almost equal to the temperature and the lower the humidity of the air, the lower the air humidity.) The reduced rate drying region requires energy for separating the interaction between the substance contained in the wet paint film and water. Since the moisture movement is hindered by voids that start to form, the movement speed of water and solvent in the wet coating film is lower than the evaporation speed of water and solvent from the surface of the wet coating film, and the latent heat of evaporation is gradually lost. This is a region where the surface temperature of the coating layer is higher than the wet bulb temperature, and the drying end point is not deprived of latent heat of vaporization.Therefore, the surface temperature of the coating layer is equal to the temperature of the dry air. means.

  In the present invention, as a method of treating the coating film to be the ink receiving layer with a treatment liquid mainly containing a polar solvent, a method of immersing in a treatment liquid in a treatment liquid storage tank, a solution fed from the treatment liquid storage tank Any of the methods for applying the treated liquid to the coating film to be the ink receiving layer may be used. 1 to 3 show schematic views showing an example of a manufacturing apparatus typically used in the second step of the present invention, but the present invention is not limited to this. As described above, the second step of the present invention is preferably carried out after the ink-receiving layer coating solution applied in the first step is gelled. At this stage, the ink is applied to the coating film that becomes the ink-receiving layer. Although the acceptability is not expressed, in the following description of FIGS. 1 to 3, it is referred to as an ink receiving layer for convenience.

The manufacturing apparatus of FIG. 1 is a manufacturing apparatus used for a method of processing by immersing an ink receiving layer in a processing liquid storage tank. In FIG. 1, the web 100 coated with the ink receiving layer coating liquid by a coating apparatus (not shown) is conveyed in the direction of the arrow in the figure, and the treatment liquid 5 is stored by the roll 1 and the submerged roll 2. It is conveyed into the liquid storage tank 6. The web 100 moves in the treatment liquid storage tank 6 and is treated with the treatment liquid 5, and then the excess treatment liquid 50 adhered to the surface of the web 100 is removed by the treatment liquid squeeze rolls 3 and 4. 7, the product is transported and dried in a drying device (not shown) such as a drying device having an air dryer, and the second step is completed. The pressure when scraping off the processing liquid 5 with the processing liquid squeeze rolls 3 and 4 is preferably 100 to 10,000 mmH ₂ O. The surplus processing liquid 50 removed by the processing liquid squeeze rolls 3 and 4 falls downward and is collected in the processing liquid storage tank 6. In FIG. 1, the ink receiving layer is located above the web 100.

  The processing liquid 5 is supplied to the processing liquid storage tank 6 from a replenishing processing liquid storage tank (not shown) via the gear pump 15 and the liquid feeding pipe 16 according to the processing area of the web 100. The processing area of the web 100 can be calculated from the width of the web 100 and the conveyance speed. The left side surface of the treatment liquid storage tank 6 is lower than the right side surface. As a result, when a certain amount or more of the processing liquid 5 is replenished, the processing liquid 5 exceeding the capacity of the processing liquid storage tank 6 is discharged from the left side surface and then discarded. In FIG. 1, the processing liquid 5 is discharged by lowering the left side surface. However, for example, the processing liquid 5 can be discharged by providing a through hole above the left side surface, or the entire left side surface can be lowered. At least a part of the processing liquid 5 may be discharged in a groove shape.

  The manufacturing apparatus shown in FIG. 2 is a manufacturing apparatus used for a method of applying a processing liquid sent from a processing liquid storage tank to an ink receiving layer for processing. In FIG. 2, the web 100 coated with the ink receiving layer coating liquid by a coating device (not shown) is transported in the direction of the arrow in the drawing by the transport rolls 21 and 22, and the transport rolls 21 and 22 and the squeeze rolls 3 and 4. In this position, the web 100 is treated with the treatment liquid 5 flowing out from the treatment liquid supply pipe 30 provided with a plurality of treatment liquid supply ports below. Thereafter, the excess processing liquid 50 adhering to the surface is removed by the processing liquid squeezing rolls 3 and 4, transported to a drying device (not shown) and dried, and the second step is completed. In FIG. 2, the treatment liquid supply pipe 30 provided with a plurality of treatment liquid supply ports is described below. However, instead of this, for example, a treatment in a form in which a plurality of spray nozzles are provided along the width direction of the web 100. A liquid supply pipe may be used.

In FIG. 2, the processing liquid 5 stored in the processing liquid storage tank 6 is supplied to a processing liquid supply pipe 30 provided with a plurality of processing liquid supply ports below through a gear pump 17 and a liquid feeding pipe 18. The After the processing liquid 5 flowing out from the processing liquid supply pipe 30 falls on the web 100, it falls from both ends of the web 100 and is circulated and returned to the processing liquid storage tank 6. The pressure when scraping off the processing liquid 50 adhering to the surface of the web 100 with the processing liquid squeezing rolls 3 and 4 is preferably 100 to 10,000 mmH ₂ O. The processing liquid 5 to be replenished according to the processing area of the web 100 is supplied from a replenishing processing liquid storage tank (not shown) into the processing liquid storage tank 6 through the gear pump 15 and the liquid feeding pipe 16. In addition, the discharge method of the process liquid 5 exceeding the capacity | capacitance of the process liquid storage tank 6 is the same as that of the manufacturing apparatus of FIG.

  The processing apparatus of FIG. 3 is an example of a manufacturing apparatus provided with air knives 31 and 32 instead of the processing liquid squeeze rolls 3 and 4 of FIG.

In the processing of the second step of the present invention, it is preferable that the processing liquid 5 to be replenished in the processing liquid storage tank 6 according to the processing area of the web 100 is supplied with a new processing liquid that is not used for processing. The amount of the replenisher to be used is preferably 40 to 100 ml per 1 m ^{2 of the} ink receiving layer to be processed. If the amount is less than this range, a sufficient effect of the treatment liquid can be obtained at the start of production, but the effect is reduced due to an increase in the concentration of components eluted with the treatment of the ink receiving layer and volatilization of some components of the treatment liquid. In some cases, an ink jet recording material having a stable quality cannot be obtained. If the amount is larger than this range, a stable quality ink jet recording material can be obtained, but a large amount of processing liquid is required, and a large amount of used processing liquid (waste liquid) is generated.

  The processing time in the second step of the present invention is within 3 seconds. When the treatment time exceeds 3 seconds, the wet treatment with the treatment liquid mainly containing a polar solvent is sufficiently performed, but on the other hand, the line speed becomes slow or it is necessary to prepare a huge storage tank. In addition, the treatment temperature in the present invention, that is, the temperature of the treatment liquid, needs to be 30 to 80 ° C. If the temperature is lower than this range, the effect of the wet treatment is hardly exhibited, and the treatment speed is reduced when a sufficient effect is to be exhibited. When the temperature is higher than this range, a hydrophilic binder or a cationic fixing agent contained in the ink receiving layer described later may be dissolved in the processing liquid, or the solvent of the processing liquid may be evaporated to affect the processing. May happen.

  The drying environment in the second step may be set appropriately as an efficient drying environment, but is preferably 10 to 40 ° C. Moreover, you may repeat a 2nd process in multiple times as needed.

  In the present invention, it is necessary that the concentration of the remaining cross-linking agent in the treatment liquid storage tank is 10 g / L or less. If it exceeds 10 g / L, a difference in quality from the ink jet recording material obtained at the start of production occurs, making it difficult to produce an ink jet recording material with stable quality.

  The treatment liquid used in the second step of the present invention is a treatment liquid mainly containing a polar solvent, and specifically includes water, an acidic solution, a neutral to basic treatment liquid, and the like. For example, when an acidic solution is used, the effect of improving the fixing property of the ink to the receiving layer and high-humidity bleeding can be obtained. In addition, when a neutral to basic treatment solution is used, the effect of improving transport cracking when transported by a front-side paper feed printer is improved by improving the discharging effect of the crosslinking agent, and the effect of improving bronzing is obtained. It is done.

  Water of various grades such as tap water, ion-exchanged water, mineral water, and ultrapure water for electronic industry can be used, but the content of water-soluble components that are preferably purified more than ion-exchanged water Is preferably 100 ppm or less of water.

  As the acid to be contained in the acidic solution, either an organic acid or an inorganic acid can be used. Examples include hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, oxalic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, phthalic acid, sulfophthalic acid, citric acid, malonic acid, Examples include malic acid and succinic acid. A polar solvent is used as a solvent for dissolving the acid. For example, water, methanol, ethanol, propanol, acetonitrile, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, sulfolane, etc. Can be mentioned. Among these, water or an alcohol solvent is preferable, and water is particularly preferable. The concentration of the acid is 0.01 to 50% by mass, preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass. In the present invention, mainly containing a polar solvent means that 50% by mass or more of the amount of the solvent component contained in the treatment liquid is a polar solvent, preferably 80% by mass or more, more preferably 90% by mass. % Or more is preferably a polar solvent.

  0.01-50 mass% is preferable and, as for the density | concentration of the basic compound which the processing liquid which has neutrality-basicity contains, 0.1-20 mass% is more preferable. Examples of the basic compound used include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium phosphate, and phosphoric acid. Basic inorganic compounds such as sodium monohydrogen, aqueous ammonia, methylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, piperidine, diazabicyclooctane, diazabicycloundecene, pyridine, quinoline, Examples include basic organic compounds such as picoline, lutidine, collidine, and alkali metal salts of organic acids such as lithium benzoate and potassium phthalate. Moreover, as a solvent to be used, the same solvent as that contained in the acidic solution is preferably used.

  In the first step of the present invention, the coating method for applying the coating solution for the ink receiving layer on the support is as follows: slide bead coater, curtain coater, extrusion coater, air knife coater, rod coater, blade coater, gravure coater, etc. These coating apparatuses can be used alone or in combination.

  The ink receiving layer coating solution used in the first step of the present invention preferably contains a hydrophilic binder. As such a hydrophilic binder, polyvinyl alcohol, polyethylene glycol, starch, dextrin, carboxymethyl cellulose, polyvinyl pyrrolidone, polyacrylic acid ester and derivatives thereof are used, and particularly preferable resin binder is completely or partially saponified polyvinyl. It is alcohol. Particularly preferred among polyvinyl alcohols are those having a saponification degree of 80% or more, or those completely saponified. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferable.

  The ink-receiving layer coating liquid used in the first step preferably contains inorganic fine particles together with a hydrophilic binder. In particular, a void-type ink receiving layer having extremely high ink absorbability can be obtained by mainly containing inorganic fine particles in the coating liquid for the ink receiving layer. Here, “mainly” means that the inorganic fine particles are contained in an amount of 50% by mass or more, more preferably 60% by mass or more, based on the total solid content of the ink-receiving layer coating solution.

  The inorganic fine particles contained in the ink receiving layer coating liquid of the present invention include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, titanium dioxide, zinc oxide, zinc hydroxide, calcium silicate, magnesium silicate, synthetic silica, Alumina, alumina hydrate, magnesium hydroxide and the like can be mentioned, and a mixture of two or more of these can be mentioned. The average secondary particle diameter of these inorganic fine particles is preferably 500 nm or less, and thereby excellent color developability can be obtained. Among these, synthetic silica, alumina, or alumina hydrate is preferable, and these inorganic fine particles can provide a high printing density and a clear image. More preferable inorganic fine particles in the present invention are amorphous synthetic silica, alumina, or alumina hydrate.

  Amorphous synthetic silica can be roughly classified into wet method silica and gas phase method silica depending on the production method. Vapor phase silica is also called a dry method as opposed to a wet method, and is generally made by a flame hydrolysis method. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane can be used alone or in silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state. Vapor phase silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd.

  Wet method silica is further classified into precipitation method silica, gel method silica, and sol method silica according to the production method. Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the silica particles that have grown are agglomerated and settled, and are then commercialized through filtration, water washing, drying, pulverization and classification. The secondary particles of silica produced by this method become loosely agglomerated particles, and particles that are relatively easy to grind are obtained. The precipitated silica is commercially available, for example, as a nip seal from Tosoh Silica Co., Ltd., as a Toku Seal from Tokuyama Co., Ltd., and as a fine seal. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. During the ripening, the fine particles dissolve and reprecipitate so as to bind other primary particles, so that the distinct primary particles disappear and form relatively hard aggregated particles having an internal void structure. For example, commercially available as Toyo Silica Co., Ltd. as nip gel, from Mizusawa Chemical Industry Co., Ltd. as Mizukasil, from Grace Japan Co., Ltd. as syloid and silo jet. The sol silica is also called colloidal silica, and is obtained by heating and aging a silica sol obtained through metathesis of sodium silicate acid or through an ion exchange resin layer. For example, it is commercially available as Snowtex from Nissan Chemical Industries, Ltd. Yes.

The vapor phase silica that can be used in the present invention will be described. The average primary particle diameter of the vapor phase silica used in the present invention is preferably 30 nm or less, and preferably 15 nm or less in order to obtain higher gloss. More preferably, an average primary particle diameter of 3 to 15 nm and a specific surface area by BET method of 200 m ² / g or more (preferably 250 to 500 m ² / g) are used. The average primary particle diameter as used in the present invention refers to the average particle diameter obtained by observing fine particles with an electron microscope and taking the diameter of a circle equal to the projected area of each of 100 primary particles present within a certain area as the particle diameter of the particles. The BET method referred to in the present invention is one of the powder surface area measurement methods by the vapor phase adsorption method, and is a method for obtaining the total surface area of a 1 g sample from the adsorption isotherm, that is, the specific surface area. is there. Usually, nitrogen gas is often used as the adsorbed gas, and the most frequently used method is to measure the amount of adsorption from the change in pressure or volume of the gas to be adsorbed. The most prominent expression for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, and Teller equation, called the BET equation, which is widely used for determining the surface area. The adsorption amount is obtained based on the BET equation, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.

  In order to make the average secondary particle diameter of the vapor phase method silica not more than 500 nm, more preferably 10 to 300 nm, the vapor phase method silica and the dispersion medium are premixed by ordinary propeller stirring, turbine type stirring, homomixer type stirring, etc. Then, it is preferable to perform dispersion using a media mill such as a ball mill, a bead mill, or a sand grinder, a high pressure homogenizer, a pressure disperser such as an ultra high pressure homogenizer, an ultrasonic disperser, a thin film swirl disperser, or the like. . The average secondary particle diameter as used in the present invention can be determined by photographing an ink receiving layer of the obtained recording material with an electron microscope. For simplicity, a laser scattering type particle size distribution meter (for example, ( The number median diameter can be measured using LA920 manufactured by HORIBA, Ltd. As the vapor phase method silica, those having an average secondary particle diameter dispersed to 500 nm or less in the presence of a cationic polymer can be preferably used.

  Examples of the cationic polymer used for the dispersion of the vapor phase silica include polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, JP-A-59-33176, JP JP 59-33177, JP 59-1555088, JP 60-11389, JP 60-49990, JP 60-83882, JP 60-109894. JP, 62-198493, JP 63-49478, JP 63-115780, JP 63-280681, JP 1-40371, JP 6-6 No. 234268, JP-A-7-125411, JP-A-10-19376, and the like. Polymers having Moniumu base is preferably used. In particular, diallylamine derivatives are preferably used as the cationic polymer. In terms of dispersibility and dispersion viscosity, the molecular weight of these cationic polymers is preferably about 2,000 to 100,000, and particularly preferably about 2,000 to 30,000. The amount of the cationic polymer used is preferably in the range of 1 to 10% by weight relative to the vapor phase silica.

  Next, the wet process silica that can be used in the present invention will be described. The wet method silica preferably used in the present invention is precipitation method silica or gel method silica. These silica powders preferably have an average primary particle size of 50 nm or less, more preferably 3 to 40 nm, and an average aggregate particle size (secondary particle size) of 5 to 50 μm. In the present invention, these wet process silica is used, for example, a media mill such as a ball mill, a bead mill, a sand grinder, a pressure disperser such as a high pressure homogenizer, an ultrahigh pressure homogenizer, an ultrasonic disperser, and a thin film swirl disperser. By doing so, an average secondary particle diameter in an aqueous medium is preferably 500 nm or less, more preferably 10 to 300 nm. The above pulverization is preferably performed in the presence of a cationic compound polymer.

  Since the wet process silica produced by a normal method has an average aggregate particle diameter of 1 μm or more, it is used after being pulverized. In order to set the average secondary particle diameter of the wet method silica to 500 nm or less, a wet dispersion method in which silica dispersed in an aqueous medium is mechanically pulverized can be preferably used. At this time, the increase in the initial viscosity of the dispersion is suppressed, high concentration dispersion is possible, and the pulverization / dispersion efficiency is increased so that the particles can be further pulverized. Therefore, the oil absorption is 210 ml / 100 g or less, the average aggregated particle diameter It is preferable to use precipitated silica of 5 μm or more. By using a high-concentration dispersion, the productivity of the recording material is also improved. The oil absorption is measured based on the description of JIS K-5101.

  As a method for pulverizing the wet method silica used in the present invention, the same method as the dispersion of the vapor phase method silica can be used. Moreover, the same thing as the cationic polymer used for dispersion | distribution of the said vapor phase method silica can be used.

  As the wet process silica used in the ink receiving layer coating liquid of the present invention, precipitated silica is preferable. As described above, precipitated silica is suitable for pulverization because its secondary particles are loosely agglomerated particles.

  Alumina or hydrated alumina suitably used in the present invention is aluminum oxide or a hydrated product thereof, which may be crystalline or amorphous, and has an amorphous shape, a spherical shape, a plate shape, or the like. What is used is used. Either of them may be used or may be used in combination.

  As the alumina oxide that can be used in the present invention, γ-alumina, which is a γ-type crystal of aluminum oxide, is preferable, and δ group crystal is particularly preferable. γ-alumina can make primary particles as small as about 10 nm. Usually, secondary particles of several thousand to several tens of thousands of nm are preferably used with an ultrasonic wave, a high-pressure homogenizer, a counter collision type jet crusher, or the like. An average secondary particle diameter of 500 nm or less, more preferably about 50 to 300 nm can be used.

The alumina hydrate that can be used in the present invention is represented by a constitutional formula of Al ₂ O ₃ .nH ₂ O (n = 1 to 3). The hydrated aluminum oxide can be obtained by a known production method such as hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali, hydrolysis of aluminate, and the like. The average secondary particle diameter of the alumina hydrate used in the present invention is preferably 500 nm or less, more preferably 10 to 300 nm.

  As the alumina and alumina hydrate used in the present invention, those dispersed by a known dispersant such as acetic acid, lactic acid, formic acid, methanesulfonic acid, hydrochloric acid, nitric acid are preferably used.

  The mass ratio of the hydrophilic binder to the inorganic fine particles in the ink receiving layer coating solution is preferably in the range of 5 to 30% by mass, particularly preferably 5 to 25% by mass.

  It is preferable that the wet coating film coated with the ink receiving layer coating liquid or the ink receiving layer coating liquid used in the present invention contains a crosslinking agent. Examples of the crosslinking agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5- Triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, US Pat. N-methylol compounds as described in US Pat. No. 732,316, isocyanates as described in US Pat. No. 3,103,437, aziridine compounds as described in US Pat. Nos. 3,017,280 and 2,983,611 Carbodiimide compounds as described in US Pat. No. 3,100,704, US Pat. , 091,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, boric acid and boric acid inorganic hardeners, etc. These can be used alone or in combination of two or more. Of these, boric acid or borates are preferable, and specifically, orthoboric acid, metaboric acid, hypoboric acid, tetraboric acid, pentaboric acid, and salts thereof (for example, sodium salt, potassium salt, ammonium salt, etc.).

  In the first step, the content of the crosslinking agent is preferably 10 to 30% by mass, more preferably 15 to 25% by mass with respect to the hydrophilic binder in the ink receiving layer.

  The ink receiving layer coating liquid of the present invention preferably contains a cationic fixing agent in order to improve color development and water resistance. As the cationic fixing agent in the present invention, various cationic polymers used for dispersion or pulverization of the above-mentioned gas phase method silica and wet method silica and various polyvalent metals can be used. It is preferable to use a water-soluble polyvalent metal typified by a reactive zirconium compound. These compounds may be any of inorganic salts, single salts and double salts of organic acids, metal complexes, and the like.

  As the water-soluble aluminum compound that can be used in the present invention, for example, aluminum chloride or a hydrate thereof, aluminum sulfate or a hydrate thereof, ammonium alum and the like are known as inorganic salts. Furthermore, a basic polyaluminum hydroxide compound which is an inorganic aluminum-containing cationic polymer is known.

Among these water-soluble aluminum compounds, those that can be stably added to the coating solution for forming the ink receiving layer are preferable, and a basic polyaluminum hydroxide compound is preferably used. The main component of this compound is represented by the following formula 1, 2 or 3, for example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ⁴⁺ , [Al ₁₃ (OH) ₃₄ ] ⁵⁺ , It is a water-soluble polyaluminum hydroxide that stably contains a basic and high-molecular polynuclear condensed ion such as [Al ₂₁ (OH) ₆₀ ] ³⁺ .

[Al ₂ (OH) _n Cl _6-n ] _m ·· Formula 1
[Al (OH) ₃ ] _n AlCl ₃ .. Formula 2
Al _n (OH) _m Cl _(3n−m) 0 <m <3n Formula 3

  These are water treatment agents under the name of polyaluminum chloride (PAC) from Taki Chemical Co., Ltd., polyaluminum hydroxide (Paho) from Asada Chemical Co., Ltd., and Riken Green Co., Ltd. It is commercially available under the name of Purachem WT and from other manufacturers for the same purpose, and various grades can be easily obtained. In the present invention, these commercially available products can be used as they are.

  The water-soluble zirconium compound used in the present invention is composed of zirconium acetate, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, zirconium carbonate / ammonium, zirconium carbonate / potassium, zirconium sulfate, zirconium fluoride, zirconium chloride, zirconium chloride octahydrate. Examples thereof include a hydrate, zirconium oxychloride, and hydroxyzirconium chloride.

  Among these water-soluble zirconium compounds, a zirconium acetate (zirconyl) compound that can be stably added to a coating solution for forming an ink receiving layer and exhibits excellent bleeding resistance is particularly preferable.

  These are commercially available as Zircozole ZA-20, ZA-30, etc. from Daiichi Rare Element Chemical Industries, Ltd., and also from Nippon Light Metal Co., Ltd.

  The total addition amount of the water-soluble aluminum compound and the water-soluble zirconium compound is preferably 10% by mass or less, more preferably 0.5 to 8% by mass with respect to the inorganic fine particles.

  The ink receiving layer coating liquid may contain various oil droplets in order to improve the brittleness of the film. Such oil droplets include hydrophobic high-boiling organic solvents (for example, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, etc.) having a solubility in water at room temperature of 0.01% by mass or less, and polymer particles ( For example, particles obtained by polymerizing one or more polymerizable monomers such as styrene, butyl acrylate, divinylbenzene, butyl methacrylate, and hydroxyethyl methacrylate) can be contained. Such oil droplets can be preferably used in the range of 10 to 50% by mass relative to the hydrophilic binder.

The ink receiving layer may be a single layer or two or more layers, and the coating amount of inorganic fine particles contained in the ink receiving layer is preferably 5 to 50 g / m ^{2, and} is preferably in the range of 15 to 40 g / m ² . More preferred.

  Examples of the support used in the present invention include absorptive supports such as high-quality paper, art paper, coated paper, cast coated paper, polyester resins such as polyethylene terephthalate, disate resin, triacetate resin, acrylic resin, polycarbonate resin, Plastic resin films such as polyvinyl chloride, polyimide resin, cellophane, celluloid, etc., and those obtained by laminating the absorbent support and the plastic resin film, polyolefin resin-coated paper coated with a polyolefin resin layer on both sides of the base paper, etc. A non-absorbable support is mentioned, and it is preferable to use a non-absorbable support. The support has a thickness of 50 to 350 μm, preferably 80 to 300 μm. In particular, a polyolefin resin-coated paper support (hereinafter referred to as a polyolefin resin-coated paper) is preferably used from the viewpoints of feel and texture.

  The polyolefin resin-coated paper will be described in detail. The water content of the polyolefin resin-coated paper used in the present invention is not particularly limited, but is preferably in the range of 5 to 9% by mass and more preferably in the range of 6 to 9% by mass from the curling property. The moisture content of the polyolefin resin-coated paper can be measured using any moisture measuring method. For example, an infrared moisture meter, an absolute dry weight method, a dielectric constant method, a Karl Fischer method, or the like can be used.

  The base paper constituting the polyolefin resin-coated paper is not particularly limited, and commonly used paper can be used. More preferably, for example, a smooth base paper used for a photographic support is preferable. As the pulp constituting the base paper, natural pulp, regenerated pulp, synthetic pulp or the like is used alone or in combination. This base paper is blended with additives such as sizing agent, paper strength enhancer, filler, antistatic agent, fluorescent whitening agent, and dye generally used in papermaking. Further, a surface sizing agent, a surface paper strength agent, a fluorescent brightening agent, an antistatic agent, a dye, an anchor agent, and the like may be applied on the surface.

Although there is no restriction | limiting in particular regarding the thickness of a base paper, The thing with good surface smoothness which applied the pressure with the calendar | calender etc. during papermaking or after papermaking is preferable, and the basic weight is 30-250 g / m. ² is preferred.

  Examples of the polyolefin resin that coats the base paper include olefin homopolymers such as low density polyethylene, high density polyethylene, polypropylene, polybutene, and polypentene, or copolymers composed of two or more olefins such as ethylene-propylene copolymer, and the like. Of various densities and melt viscosity indices (melt index) can be used alone or as a mixture thereof.

  In the resin of polyolefin resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, aluminum stearate, stearic acid Fatty acid metal salts such as magnesium, blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue, and phthalocyanine blue, magenta pigments and dyes such as cobalt violet, fast violet and manganese purple, fluorescent brighteners, ultraviolet absorbers, etc. These various additives are preferably added in appropriate combination.

  As a main method for producing a polyolefin resin-coated paper, it is produced by a so-called extrusion coating method in which a polyolefin resin is cast on a traveling base paper in a heated and melted state, and both surfaces of the base paper are coated with the resin. Further, before the resin is coated on the base paper, the base paper is preferably subjected to an activation treatment such as corona discharge treatment or flame treatment. The thickness of the resin coating layer is suitably 5 to 50 μm.

An undercoat layer is preferably provided on the side of the non-water-absorbing support on which the ink receiving layer is applied. This undercoat layer is applied and dried in advance on the surface of the non-water-absorbing support before the ink receiving layer coating solution is applied. This undercoat layer mainly contains a water-soluble polymer or polymer latex that can form a film. Preferred are water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinyl pyrrolidone and water-soluble cellulose, and particularly preferred is gelatin. Adhesion amount of the water-soluble polymer is preferably ^{10~500mg / m 2, 20~300mg / m} 2 is more preferable. Furthermore, it is preferable that the undercoat layer contains a surfactant and a hardener.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example. In addition, a part represents the mass part of solid content or a substantial component.

Example 1
<Preparation of polyolefin resin-coated paper 1>
A 1: 1 mixture of hardwood bleached kraft pulp (LBKP) and hardwood bleached sulfite pulp (LBSP) was beaten to 300 ml with Canadian Standard Freeness to prepare a pulp slurry. The sizing agent and alkyl ketene dimer were 0.5% by mass of pulp, 1% by mass of polyacrylamide as a strengthening agent, 1% by mass of cationized starch, 2% by mass of pulp, and polyamide epichlorohydrin resin by 0.1% of pulp. 5% by mass was added and diluted with water to give a 0.2% by mass slurry. This slurry was made with a long paper machine to a basis weight of 170 g / m ² , dried and conditioned to obtain a base paper for the support. A polyethylene resin composition in which 10% by mass of anatase-type titanium is uniformly dispersed with respect to a low-density polyethylene resin having a density of 0.918 g / cm ³ is melted at 320 ° C. on the printed surface side of the base paper made at 200 ° C. The resin coating layer on the ink receiving layer application surface side was provided while cooling with a cooling roll that had been finely roughened and extruded to a thickness of 30 μm per minute. On the opposite side to melt at similarly 320 ° C. The blend resin composition of the low density polyethylene resin 30 parts of a density 0.962 g / cm 70 parts high density polyethylene resin of ³ and a density 0.918 g / cm ^3, a thickness A resin coating layer was provided while cooling with a cooling roll to 25 μm. Thus, a roll-shaped polyolefin resin-coated paper 1 having a width of 1000 mm and a length of 100 m was obtained.

The polyolefin resin-coated paper 1 was subjected to high-frequency corona discharge treatment on the ink-receiving layer-coated surface side, and then the undercoat layer 1 having the following composition was coated and dried so that the gelatin content was 50 mg / m ² .

<Undercoat layer 1>
Lime-processed gelatin 100 parts Sulfosuccinic acid-2-ethylhexyl ester salt 2 parts Chrome alum 10 parts

Silica dispersion 1 was prepared as follows.
<Silica dispersion 1>
4 parts of dimethyldiallylammonium chloride homopolymer (Charol DC902P, Daiichi Kogyo Seiyaku Co., Ltd .; molecular weight 9,000) and 100 parts of gas phase method silica (average primary particle diameter 7 nm, BET specific surface area 300 m ² / g) in water And a preliminary dispersion was prepared using a sawtooth blade type disperser (blade peripheral speed 30 m / sec). Next, the obtained preliminary dispersion was passed twice through a pressure homogenizer under the condition of 40 MPa to obtain a silica dispersion 1 having a solid content concentration of 20%. When the dispersion was measured with a laser diffraction / scattering particle size distribution analyzer (HORIBA LA-920), the average secondary particle diameter of the vapor phase silica was 130 nm.

As a first step, a coating speed of 50 m is applied using a slide bead coating apparatus so that the coating amount of the ink receiving layer 1 having the following composition is 25 g / m ² on the surface on which the undercoat layer 1 is applied. After cooling at 5 ° C. for 30 seconds, it was dried at 35 ° C. and 10% RH.
<Ink-receiving layer coating solution 1>
Silica dispersion 1 (as silica solid content) 100 parts polyvinyl alcohol 23 parts (saponification degree 88%, average polymerization degree 3500)
4 parts of boric acid The ink receiving layer coating solution 1 was adjusted with ion exchange water to a solid content concentration of 13% by mass.

After the surface temperature of the coating film reaches 35 ° C., using the manufacturing apparatus shown in FIG. 1 as the second step, the temperature of the processing liquid is set in the processing liquid storage tank into which the processing liquid 1 having the following composition is charged. Treated at 60 ° C. for 1.2 seconds. The treatment liquid storage tank 6 in FIG. 1 has a length of 300 mm in the traveling direction of the web 100 to which the ink receiving layer coating liquid 1 is applied, a length in the width direction of the web 100 of 1200 mm, and the left side from which the treatment liquid 5 is discharged. The height of the side surface is 500 mm. The submerged roll 2 had a diameter of 200 mm and a width of 1100 mm, and the amount of the processing liquid 5 required to fill the processing liquid storage tank 6 was 115 L. The line speed of the web 100 is 50 m / min. Immediately after leaving the treatment liquid storage tank 6, excess treatment liquid was squeezed by bringing the treatment liquid squeeze rolls 3 and 4 into contact with the web 100 at a pressure of 300 mmH ₂ O, and then dried at 35 ° C.

The treatment liquid storage tank 6 was replenished with 2.5 L / min of treatment liquid (50 ml with respect to 1 m ^{2 of} ink receiving layer). After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 51% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Moreover, as a result of collecting drainage just before the end of production and measuring the amount of boric acid in the treatment liquid by the azomethine H method, the residual boric acid concentration in the treatment liquid was 0.33 g / L.
<Processing liquid 1>
Ion exchange water (pH = 7.0)

(Example 2)
In the same manner as in Example 1, after applying the coating liquid 1 for the ink receiving layer on the surface on which the undercoat layer 1 was applied and drying, the surface temperature of the coating film reached 35 ° C., and then the manufacturing apparatus shown in FIG. An ink jet recording material was produced. The capacity of the treatment liquid storage tank 6 is 3 L, and the treatment liquid 1 used in Example 1 was added here. The treatment liquid 1 is fed by a liquid feed pipe 18 and a gear pump 17 to a treatment liquid supply pipe 30 having a plurality of treatment liquid supply ports, and is applied to the coating film to which the ink receiving layer coating liquid 1 is applied from the treatment liquid supply port. Then, it circulates back to the treatment liquid storage tank 6. The temperature of the circulating treatment liquid 1 was 60 ° C. The treatment liquid 1 discharged from the treatment liquid supply pipe 30 has a discharge pressure of 0.1 MPa and a discharge amount of 600 ml / min (20 ml with respect to 1 m ^{2 of the} ink receiving layer). The distance from the position lowered to the squeezing rolls 3 and 4 was 1.2 m, and the line speed of the web 100 was 60 m / min (processing time was 1.2 seconds). The treatment liquid storage tank 6 was supplemented with the treatment liquid 1 at 3.0 L / min (50 ml per 1 m ^{2 of the} ink receiving layer). After continuously producing 100 m ² in this way, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. As a result, boric acid remaining in the ink receiving layer was obtained. Was 66 mass% with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected at the end of production, and the boric acid content of the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 6.4 g / L.

(Example 3)
A manufacturing apparatus as shown in FIG. 3 was used as the second step. The treatment liquid storage tank 6 in FIG. 3 has a length of 700 mm in the traveling direction of the web 100 coated with the ink receiving layer, a length in the width direction of the web 100 of 1200 mm, and the height of the left side surface from which the treatment liquid 5 is discharged. Is 400 mm, and the total length of the web 100 while it is in contact with the processing liquid is 1000 mm. The submerged roll 2 had a diameter of 200 mm and a width of 1100 mm, and the amount of the processing liquid 5 required to fill the processing liquid storage tank 6 was 300 L. The line speed of the web 100 is 50 m / min. Immediately after coming out of the treatment liquid storage tank 6, excess treatment liquid was squeezed out by bringing the air knives 31 and 32 into contact with the web 100 at a pressure of 300 mmH ₂ O, and then dried at 35 ° C. The treatment liquid 1 was replenished with 3.0 L / min (50 ml with respect to 1 m ^{2 of the} ink receiving layer). An inkjet recording material of Example 3 was produced in the same manner as Example 1 except for the above. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 66% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 0.13 g / L.

Example 4
An ink jet recording material of Example 4 was produced in the same manner as in Example 2 except that the replenishing amount of the treatment liquid of Example 2 was 4.8 L / min (80 ml per m ^{2 of} ink receiving layer). After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 63% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected at the end of production, and the boric acid content of the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 4.6 g / L.

(Example 5)
An inkjet recording material of Example 5 was produced in the same manner as Example 2 except that the processing temperature of Example 2 was set to 70 ° C. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 56% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected at the end of production, and the boric acid content of the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 8.0 g / L.

(Example 6)
An inkjet recording material of Example 6 was produced in the same manner as Example 2 except that the processing temperature of Example 2 was set to 40 ° C. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 72% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. In addition, the waste liquid was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 5.1 g / L.

(Example 7)
The inkjet recording material of Example 7 is produced in the same manner as in Example 2 except that the distance from the position where the processing liquid descends from the processing liquid supply pipe 30 (shower) of Example 2 to the squeeze rolls 3 and 4 is 2 m. did. At this time, the time during which the ink receiving layer was immersed in the processing liquid, that is, the processing time was 2 seconds. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 60% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 7.7 g / L.

(Example 8)
An ink jet recording material of Example 8 was produced in the same manner as in Example 2 except that the treatment liquid 1 of Example 2 was changed to the treatment liquid 2 having the following composition. After 100 m ² of production from the production of the polyolefin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The remaining boric acid was 62 mass% with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. In addition, the waste liquid was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 7.0 g / L.
<Processing liquid 2>
0.82 g / L sodium acetate aqueous solution (pH = 8.5)

Example 9
An inkjet recording material of Example 9 was produced in the same manner as in Example 2 except that the treatment liquid 1 of Example 2 was changed to the treatment liquid 3 having the following composition. After 100 m ² of production from the production of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining therein was 71% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 5.4 g / L.
<Processing liquid 3>
0.61 g / L acetic acid aqueous solution (pH = 3)

(Example 10)
An ink jet recording material of Example 10 was produced in the same manner as Example 2 except that the treatment liquid 1 of Example 2 was changed to the treatment liquid 4 having the following composition. After 100 m ² of production from the production of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining therein was 70% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 5.8 g / L.
<Treatment liquid 4>
1.0 g / L citric acid aqueous solution (pH = 3.2)

(Example 11)
Alumina hydrate was dispersed as follows to prepare alumina dispersion 1.
<Alumina dispersion 1>
Add 2 parts of nitric acid and 100 parts of alumina hydrate (average primary particle size 14 nm, BET specific surface area 190 m ² / g) to water, using a sawtooth blade type disperser (blade peripheral speed 30 m / sec). By dispersing, an alumina dispersion 1 having a solid content of 30% was obtained. In addition, the average secondary particle diameter of the alumina dispersion measured by a laser diffraction / scattering particle size distribution analyzer (HORIBA LA-920) was 160 nm.

As the first step of Example 2, the inkjet recording material of Example 11 was prepared in the same manner as in Example 2 except that the ink receiving layer coating liquid 1 used was changed to the ink receiving layer coating liquid 2 having the following composition. Produced. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 65% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and alumina were not substantially reduced. In addition, the drainage was collected at the end of production, and the boric acid content of the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 3.3 g / L.
<Ink-receiving layer coating solution 2>
Alumina dispersion 1 (as alumina solid content) 100 parts polyvinyl alcohol 10 parts (saponification degree 88%, average polymerization degree 3500)
Boric acid 2 parts The ink receiving layer coating solution 2 was adjusted with ion-exchanged water to a solid content concentration of 16% by mass.

(Example 12)
The polyolefin resin-coated paper 1 was subjected to high-frequency corona discharge treatment on the ink-receiving layer-coated surface side, and then the undercoat layer 1 was coated and dried so that gelatin was 50 mg / m ² . Next, an ink receiving layer coating solution 3 having the following composition was applied so that the solid content was 25 g / m ² .
<Ink-receiving layer coating solution 3>
Alumina dispersion 1 (as alumina solid content) 100 parts polyvinyl alcohol 10 parts (saponification degree 88%, average polymerization degree 3500)
The ink receiving layer coating solution 3 was adjusted to a solid content concentration of 16% by mass with ion-exchanged water.

After the ink receiving layer coating liquid 3 was applied, the following crosslinking agent composition liquid 1 was immediately applied onto the ink receiving layer so that the solid content of borax was 0.8 g / m ² and then dried. .
<Crosslinking agent composition liquid 1>
0.04 g / L Borax and 1.5 g / L ammonia mixed aqueous solution (pH = 11)

Next, as a second step, an inkjet recording material of Example 12 was produced in the same manner as Example 2 except that the treatment liquid 1 was changed to the treatment liquid 5 having the following composition. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, borax was extracted with hot water from the ink receiving layer at the end of production, and measured by the azomethine H method. Borax remaining in the receiving layer was 55% by mass with respect to the ink receiving layer formed in the first step. Since polyvinyl alcohol and silica also flowed into the treatment liquid, the solid coating amount of the ink receiving layer was 80% by mass with respect to the solid coating amount applied in the first step. Further, the waste liquid was collected just before the end of production, and the amount of borax in the treatment liquid was measured by the azomethine H method. As a result, the residual borax concentration in the treatment liquid was 4.3 g / L.
<Treatment liquid 5>
1.55 g / L aqueous ammonia solution (pH = 11)

(Comparative Example 1)
An inkjet recording material of Comparative Example 1 was produced in the same manner as Example 2 except that the second step of Example 2 was not performed.

(Comparative Example 2)
As the first step of Comparative Example 1, an ink jet recording material of Comparative Example 2 was prepared in the same manner as Comparative Example 1 except that the ink receiving layer coating liquid 1 used was changed to an ink receiving layer coating liquid 4 having the following composition. did.
<Ink-receiving layer coating solution 4>
Silica dispersion 1 (as silica solid content) 100 parts polyvinyl alcohol 23 parts (saponification degree 88%, average polymerization degree 3500)
Boric acid 2.5 parts The ink receiving layer coating solution 4 was adjusted to a solid content concentration of 13% by mass with ion-exchanged water.

(Comparative Example 3)
An inkjet recording material of Comparative Example 3 was produced in the same manner as in Example 2 except that the treatment liquid 1 of Example 2 was not replenished. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 83% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. In addition, since the drainage liquid was not discharged, the treatment liquid was collected from the storage tank 6 after the production was finished, and the boric acid amount of the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 39. It was 4 g / L.

(Comparative Example 4)
An inkjet recording material of Comparative Example 4 was produced in the same manner as in Example 2 except that the replenishing amount of the treatment liquid 1 of Example 2 was 0.9 L / min (15 ml with respect to 1 m ^{2 of the} ink receiving layer). After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 76% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, since the drainage liquid was not discharged, the treatment liquid was collected from the storage tank 6 after the production was finished, and the boric acid content of the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 12. It was 0 g / L.

(Comparative Example 5)
An inkjet recording material of Comparative Example 5 was produced in the same manner as Example 2 except that the processing temperature of Example 2 was 20 ° C. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 76% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 4.5 g / L.

(Comparative Example 6)
An inkjet recording material of Comparative Example 6 was produced in the same manner as Example 2 except that the processing temperature of Example 2 was 90 ° C. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 56% by mass with respect to the ink receiving layer formed in the first step. In addition, bubbles were generated from the waste liquid at the start of production, probably because polyvinyl alcohol had started to dissolve. Further, the drainage was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 8.3 g / L.

(Comparative Example 7)
An ink jet recording material of Comparative Example 7 is produced in the same manner as in Example 2 except that the distance from the position where the processing liquid descends from the processing liquid supply pipe 30 (shower) of Example 2 to the squeeze rolls 3 and 4 is 4 m. did. At this time, the time during which the ink receiving layer was immersed in the processing liquid, that is, the processing time was 4 seconds. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 52% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, the drainage was collected just before the end of production, and the amount of boric acid in the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 9.0 g / L.

(Comparative Example 8)
An inkjet recording material of Comparative Example 8 was produced in the same manner as in Example 9 except that the treatment liquid 3 of Example 9 was not replenished. After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. The boric acid remaining in the receiving layer was 72% by mass with respect to the ink receiving layer formed in the first step. Polyvinyl alcohol and silica were not substantially reduced. Further, since the drainage liquid was not discharged, the treatment liquid was collected from the storage tank 6 after the completion of production, and the boric acid amount of the treatment liquid was measured by the azomethine H method. As a result, the residual boric acid concentration in the treatment liquid was 15. It was 0 g / L.

(Comparative Example 9)
An inkjet recording material of Comparative Example 9 was produced in the same manner as in Example 12 except that the replenishing amount of the treatment liquid 6 of Example 12 was 0.9 L / min (15 ml with respect to 1 m ^{2 of the} ink receiving layer). After 100 m ² of production from the preparation of the polyolefin resin-coated paper 1 to the second step was performed, boric acid was extracted from the ink receiving layer at the end of production with hot water and measured by the azomethine H method. Borax remaining in the receiving layer was 61% by mass with respect to the ink receiving layer formed in the first step. Since polyvinyl alcohol and alumina also flowed into the treatment liquid, the solid coating amount of the ink receiving layer was 80% by mass with respect to the solid coating amount applied in the first step. Further, since the drainage liquid was not discharged, the treatment liquid was collected from the storage tank 6 after the production was completed, and the boric acid amount of the treatment liquid was measured by the azomethine H method. As a result, the residual borax concentration in the treatment liquid was 14. It was 9 g / L.

Among the produced ink jet recording materials, 10 m ² and 100 m ^{2 of the} produced ink jet recording material were collected from the beginning of production of Examples 1 to 8 and Comparative Examples 1 to 7, and the following evaluation was performed. The results are shown in Table 1.

<Crack on surface of ink receiving layer>
The blank paper portion was visually evaluated.
(Double-circle): A crack is not worried at all.
○: Cracks can be found when observed closely, but this is not a problem in practice.
Δ: There are some cracks.
X: A crack is conspicuous.

<Transport crack>
The ink jet recording material was conditioned for 8 hours in a 13 ° C. and 35% RH environment, black solids were printed with a front-feed ink jet printer (Photo Smart C5175 manufactured by Hewlett Packard), and cracks generated during conveyance were visually evaluated.
(Double-circle): A crack is not worried at all.
○: Although small cracks can be found when observed closely, there is no practical problem.
Δ: There are some cracks.
X: The crack is conspicuous.

<Bronzing>
A 100% cyan image was printed with an ink jet printer for dye ink (PM-G800 manufactured by Seiko Epson Corporation), and bronzing of the image area was visually observed immediately after printing.
A: I don't care at all.
○: Little concern.
Δ: Slightly generated.
X: Very conspicuous.

  From the results of Table 1, by using the method for producing an ink jet recording material according to the present invention (Examples 1 to 8), there is no crack on the surface of the ink receiving layer, and transport cracks when transported by a front feed printer and It can be seen that the inkjet recording material excellent in bronzing of dye ink can be mass-produced continuously and stably. When the 2nd process was not performed (comparative example 1), the conveyance crack at the time of conveying with a front feed printer occurred. Further, when boric acid was reduced in the first step (Comparative Example 2), surface cracks occurred after the end of the first step. When the residual crosslinker concentration in the treatment liquid exceeds 10 g / L (Comparative Examples 3 and 4), the effect of the present invention is sufficiently achieved at the start of production, but is conveyed by a front feed printer at the end of production. The conveyance cracking at the time of deterioration deteriorated, and in particular, when the residual crosslinking agent concentration was high (Comparative Example 3), bronzing was also deteriorated. When the processing temperature was too low (Comparative Example 5), a transport crack occurred when transported by the front feed printer at the end of production. Further, when the processing temperature was too high (Comparative Example 6) or when the processing time was too long (Comparative Example 7), a surface crack was generated particularly at the start of production.

The ink jet recording materials of 10 m ² and 100 m ² produced from the start of production of Examples 9 and 10 and Comparative Examples 1 and 8 were collected and evaluated as follows. The results are shown in Table 2.

<Transport crack>
The ink jet recording material was conditioned for 8 hours in a 13 ° C. and 35% RH environment, black solids were printed with a front-feed ink jet printer (Photo Smart C5175 manufactured by Hewlett Packard), and cracks generated during conveyance were visually evaluated.
(Double-circle): A crack is not worried at all.
○: Although small cracks can be found when observed closely, there is no practical problem.
Δ: There are some cracks.
X: The crack is conspicuous.

<High humidity bleeding>
After printing each line of red, green, blue, and black with a commercially available inkjet printer (manufactured by Seiko Epson Corporation, PM-G800), visually observe a sample stored in an environment of 35 ° C. and 80% RH for 3 days. The determination was made according to the following criteria.
A: There is no bleeding.
○: Slight bleeding is observed but there is no practical problem.
Δ: Bleeding is observed.
X: Remarkably blurred.

  From the results shown in Table 2, by using the method for producing an inkjet recording material according to the present invention (Examples 9 and 10), inkjet recording excellent in conveyance cracks and high-humidity bleeding of dye ink when conveyed by a front paper feed printer. It can be seen that the material can be mass-produced continuously and stably. When the 2nd process was not performed (comparative example 1), the conveyance crack at the time of conveying with a front paper feed printer and the high-humidity blot of dye ink occurred. Further, when the residual crosslinker concentration in the processing liquid exceeds 10 g / L (Comparative Example 8), the effect of the present invention is sufficiently achieved at the start of production, but is conveyed by the front sheet feed printer at the end of production. The conveyance crack at the time of doing worsened.

The ink jet recording materials of 10 m ² and 100 m ² produced from the start of production in Examples 11 and 12 and Comparative Example 9 were collected and evaluated as follows. The results are shown in Table 3.

<Ozone resistance>
After printing each thin line of red, green, blue and black with a commercially available inkjet printer (Seiko Epson Corporation, PM-G800), use an ozone generator and put it in an environment with an ozone concentration of 10 ppm and 23 ° C. and 50% RH. Stored for 1 day. Samples before and after using the ozone device were measured with a GretagMacbeth Spectrolino color difference meter (manufactured by X-rite) and judged according to the following criteria.
A: The average color difference of the four colors is less than ΔE = 5.
X: The average color difference of the four colors is ΔE = 5 or more.

  From the results in Table 3, it is possible to continuously and stably mass-produce inkjet recording materials excellent in ozone resistance of dye inks by using the method for producing inkjet recording materials according to the present invention (Examples 11 and 12). I understand that there is. Further, when the residual crosslinker concentration in the treatment liquid exceeds 10 g / L (Comparative Example 9), the effect of the present invention is sufficiently achieved at the start of production, but the treatment efficiency is reduced at the end of production, and ozone is reduced. Resistance deteriorated.

100. Web 1. 1. Drive roll Submerged guide rolls 3, 4. Treatment liquid squeeze roll 5, 50. Treatment liquid6. 6. Treatment liquid storage tank Rolls 15, 17; Gear pumps 16, 18. Liquid feeding pipes 21, 22. Transport roll 30. Treatment liquid supply pipes 31, 32. Air knife

Claims (1)

  The first step of applying the ink receiving layer coating liquid on the support, and the coating film to be the ink receiving layer obtained in the first step mainly contains the polar solvent stored in the treatment liquid storage tank A method for producing an ink jet recording material comprising at least a second step of treatment with a treatment liquid followed by drying, wherein the treatment temperature of the treatment liquid is 30 to 80 ° C., the treatment time is within 3 seconds, And the manufacturing method of the inkjet recording material characterized by the residual crosslinking agent density | concentration in a process liquid being 10 g / L or less.

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